CN108483396A - The solar energy fuel preparation system and method for electric-thermal chemical cycle coupling - Google Patents
The solar energy fuel preparation system and method for electric-thermal chemical cycle coupling Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
- C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1642—Controlling the product
- C01B2203/1647—Controlling the amount of the product
- C01B2203/1652—Measuring the amount of product
- C01B2203/1657—Measuring the amount of product the product being hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The high-efficiency solar fuel preparation system and method, the system of a kind of electrothermal chemical cycle coupling include mainly：Optically focused divides subsystem, three-step approach methane vapor reforming subsystem, high-temperature electrolysis water hydrogen manufacturing subsystem；The first solar spectral that subsystem obtains wherein is divided by optically focused and carries out three-step approach methane water reforming reaction by collecting thermal drivers three-step approach methane vapor reforming subsystem；And the second spectrum obtained drives high-temperature electrolysis water hydrogen manufacturing subsystem to carry out electrolysis water H by photovoltaic cell2Reaction；Three-step approach methane vapor reforming subsystem can provide required thermal energy, high-temperature vapor air source and reducing atmosphere for high-temperature electrolysis water hydrogen manufacturing subsystem, and the pure O that high-temperature electrolysis water hydrogen manufacturing subsystem generates2It can be directly used for three-step approach methane vapor reforming subsystem.The present invention realizes the collaboration coupling of solar heat chemistry, electrochemical process, and pure hydrogen and high-quality synthesis gas can efficiently be made, convert solar energy highly effective to hydrocarbon and hydrogen fuel.
Description
Technical field
The present invention relates to the solar energy fuel that technical field of fuel preparation more particularly to a kind of electric-thermal chemical cycle couple
Preparation system and method.
Background technology
China is the country of a rich coal, oil-poor, few gas, and fire coal can cause environment seriously to pollute.Energy problem closes
It is national economy, is the main restricting factor that current China's economy high speed develops in a healthy way, the exploitation of renewable and clean energy resource and profit
With being to solve the problems, such as this important means particularly with the rational and efficient use of solar energy.
Distribution of solar energy is extensive, but discontinuous, unstable, and it is particularly important to find a kind of method of efficient storage solar energy.
Currently, producing fuel using solar energy is directly divided solar energy collecting, fixation and the effective ways of storage, but using solar energy
Xie Shui and the fuel such as carbon dioxide preparation hydrogen and carbon monoxide, there are reaction temperatures it is high, efficiency is low the problems such as.
The fossil fuels such as methane are combined with solar energy Chemical complementation, decompose water and carbon dioxide preparation hydrogen and titanium dioxide
Carbon can effectively reduce reaction temperature, raising solar energy fuel produces efficiency.Wherein two-step method methane chemical chain is reformed to have and is not easy
Carbon distribution, the H that suitable F- T synthesis can be prepared2The advantages that high-quality synthesis gas that/CO molar ratios are 2.But two-step method methane chemical chain
Reforming oxygenated process is less by the amounts of hydrogen that water decomposition generates, and unit mass the high cost carrier of oxygen generate fuel quantity compared with
It is low.
Invention content
In view of this, the main purpose of the present invention is to provide a kind of solar energy fuel systems of electric-thermal chemical cycle coupling
Standby system and method, to solve at least one of above-mentioned the technical issues of referring at least partly.
In order to achieve the above objectives, technical scheme is as follows：
As one aspect of the present invention, a kind of solar energy fuel preparation system of electric-thermal chemical cycle coupling is provided,
Including：Optically focused divides subsystem, and optically focused and frequency dividing are carried out to solar spectral, to form the first light beam and the second light beam；Three steps
Method methane vapor reforming subsystem, including：Heat collection unit converts first light beam to thermal energy；And reforming reaction list
Member, including：Reduction reactor is thermally connected with the heat collection unit, as carrier of oxygen MOzWith methane reaction generate hydrocarbon fuel and
Carrier of oxygen MOxContainer；Oxidation reactor, as vapor and carrier of oxygen MOxReaction generates MOyWith the container of hydrogen, Yi Jizai
Oxidation reactor, as carrier of oxygen MOyIt is reacted with oxygen and generates carrier of oxygen MOzContainer, wherein the reduction reactor is connected to
Oxidation reactor to oxidation reactor to convey MOx, the oxidation reactor, which is connected to, reoxidizes reactor with anti-to reoxidizing
Device is answered to convey MOy, it is described reoxidize reactor be connected to reduction reactor with to reduction reactor convey MOz；High-temperature electrolysis water system
Hydrogen subsystem, including：Photovoltaic generation unit converts second light beam to electric energy；And electrolytic tank of solid oxide, with institute
Photovoltaic generation unit electrical connection is stated, and is thermally connected with the oxidation reactor, as the heat effect transmitted in oxidation reactor
Under to vapor carry out electrolytic hydrogen production reaction generate hydrogen fuel container；The electrolytic tank of solid oxide is further connected to
It is described to reoxidize reactor and oxidation reactor, with to reoxidizing reactor conveying oxygen and the hydrogen that exports oxidation reactor
The gaseous mixture of gas and unreacted vapor is passed through electrolytic tank of solid oxide；And heat exchange subsystem, respectively with the reformation
Reaction member, electrolytic tank of solid oxide are connected by pipeline, to the reforming reaction unit output hydrocarbon fuel, hydrogen and
Unreacted vapor and the electrolytic tank of solid oxide output hydrogen and the vapor not being electrolysed completely heat into
Row recycling.
As another aspect of the present invention, a kind of use solar energy fuel preparation system as described above is provided and is fired
The method for expecting to prepare, including：
Step 1：Optically focused and frequency dividing are carried out to solar spectral, the first light beam and the second light beam are formed, wherein by the first light
Beam is converted into thermal energy, converts the second light beam to electric energy；
Step 2：Using the thermal energy three-step approach methane vapor reforming is carried out by raw material of methane, vapor and the carrier of oxygen
Hydrocarbon fuel and hydrogen is obtained by the reaction, and the heat of the hydrocarbon fuel, hydrogen and unreacted vapor is recycled,
Described in three-step approach methane-steam reforming include：Carrier of oxygen MOzHydrocarbon fuel and carrier of oxygen MO are generated with methane reactionx、
Vapor and carrier of oxygen MOxReaction generates MOyWith hydrogen and carrier of oxygen MOyIt is reacted with oxygen and generates carrier of oxygen MOz；
Step 3：The gaseous mixture of hydrogen and unreacted vapor is passed through electrolytic tank of solid oxide, utilizes the electric energy
And vapor and carrier of oxygen MOxThe waste heat of reaction carries out electrolytic hydrogen production reaction, to obtain hydrogen fuel and oxygen, and to described
The hydrogen of electrolytic tank of solid oxide output and the heat for the vapor not being electrolysed completely are recycled；
Step 4：Using the oxygen obtained by step 3 as carrier of oxygen MO in raw material and step 2yIt carries out reaction and generates the carrier of oxygen
MOz。
Based on the above-mentioned technical proposal, the invention has the advantages that：
1, it is the first light beam and the second light beam by solar spectral frequency dividing, converts the first light beam to thermal energy for three-step approach first
Alkane steam reforming subsystem carries out thermochemical cycles reaction, converts the second light beam to electric energy high-temperature electrolysis water hydrogen manufacturing subsystem
Electrolytic hydrogen production reaction is carried out, the oxidation reaction of three-step approach methane vapor reforming can be that electrolytic tank of solid oxide (SOEC) is electrolysed
Thermal energy and high-temperature vapor, make thermal chemical reaction waste heat make full use of, avoid the additional consumption in electrolytic hydrogen production process needed for providing
Can, it improves and decomposes water, and the pure O of SOEC electrolysates2Can be directly used for three-step approach methane vapor reforming reoxidizes reaction
Process keeps the carrier of oxygen fully oxidized, can realize making full use of for the high cost carrier of oxygen, therefore with methane reactions more as possible
The collaboration coupling for realizing heat chemistry and electrochemistry, improves the utilization ratio of solar spectral.
2, by dividing solar spectral, the generating efficiency of photovoltaic cell is improved, light is reduced and turns electric loss, to make too
Sun can be hydrogen by electrolysis water Efficient Conversion.
3, three-step approach methane vapor reforming release hydrogen is passed through electrolytic cell the moon together with the complete vapor of unreacted
Pole provides the reducing atmosphere to play a protective role for cathode, improves solar energy electrolyzing water H2Efficiency and effect.
4, CH can be made4It is converted to hydrocarbon fuel, i.e. H2And CO, and H2: CO molar ratios are 2, meet F- T synthesis ratio, keep away
Exempt from the separating energy consumption and hydrosphere transformation energy consumption of downstream chemical utilization process.
Description of the drawings
Fig. 1 is a kind of solar energy fuel preparation system schematic diagram of electric-thermal chemical cycle coupling of the embodiment of the present invention.
In above-mentioned attached drawing, reference numeral concrete meaning is as follows：
1- Salar light-gathering frequency dividers；2- First Heat Exchangers；
3- reduction reactors；4- oxidation reactors；
5- reoxidizes reactor；6- electrolytic tank of solid oxide；
The second heat exchangers of 7-；8- third heat exchangers；
The 4th heat exchangers of 9-；10- photovoltaic cells；
11- current dividers.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
Fuel efficiency is produced to improve solar energy, hydrogen production by water decomposition amount is improved, improves prepared by the unit mass carrier of oxygen
Fuel quantity, the present invention propose a kind of the high-efficiency solar fuel preparation system and method for the coupling of electric-thermal chemical cycle.
Fig. 1 is the solar energy fuel preparation system schematic diagram of electric-thermal chemical cycle of embodiment of the present invention coupling, the system packet
Include optically focused frequency dividing subsystem, three-step approach methane vapor reforming subsystem, high-temperature electrolysis water hydrogen manufacturing subsystem and heat exchange subsystem
System.
Wherein solar spectral is divided into the first light beam and the by optically focused frequency dividing subsystem by Salar light-gathering frequency divider 1
Two light beams, wherein the second light beam wavelength ranges preferably from 600~900nm shortwaves for generating electricity, the wave-length coverage of the first light beam is then
Remaining wave band is contained, thermal-arrest is used for；Wherein generate electricity generation electric energy for driving SOEC electrolysis waters H2Subsystem, thermal-arrest production
Raw thermal energy is used to drive three-step approach methane vapor reforming subsystem,
Three-step approach methane vapor reforming subsystem includes heat collection unit (being not drawn into figure) and reforming reaction unit,
Wherein heat collection unit converts the first light beam to thermal energy；Reforming reaction unit, it is anti-for carrying out three-step approach methane vapor reforming
It answers, specifically include reduction reactor 3, oxidation reactor 4 and reoxidizes reactor 5, wherein：
Reduction reactor 3 is thermally connected with heat collection unit, methane and carrier of oxygen MO in reduction reactor 3zIn heat collection unit
Thermal energy effect under reacted, by MOzIt is reduced to MOx, and generate CO, H2、CO2、H2The products such as O, wherein CO, H2It is as hydrocarbon
Fuel can be used for F- T synthesis, carrier of oxygen MOzSelected from cerium oxide, zinc oxide, copper oxide, nickel oxide or the Ca-Ti ore type carrier of oxygen
In it is one or more.
Vapor and carrier of oxygen MO in oxidation reactor 4xIt is reacted, by carrier of oxygen MOxIt is initially oxidised as MOy, and it is raw
At hydrogen, the preliminary oxidation degree of the carrier of oxygen can be adjusted in the dosage by changing vapor, in oxidation reactor 4
Reaction is exothermic reaction, and there is no need to heat collection units to carry out high temperature driven to it.
The carrier of oxygen MO in reoxidizing reactor 5yIt is reacted with oxygen, by carrier of oxygen MOyComplete oxidation is MOz, again
Reaction in oxidation reactor 5 is exothermic reaction, and there is no need to heat collection units to carry out high temperature driven to it, preferably, oxygen again
Change reactor 5 and reduction reactor 4 is thermally connected, to transmit the residual heat of reaction reoxidized in reactor 5 to reduction reactor 4
Wherein reduction reactor 3 is connected to convey MO to oxidation reactor 4x, oxidation reactor 4, which is connected to, to be reoxidized instead
Answer device with to reoxidize reactor 5 convey MOy, reoxidize reactor 5 and be connected to reduction reactor to be conveyed to reduction reactor 3
MOZ,, thermochemical cycles process is completed, unit carrier of oxygen MO is madezIt can be with more methane reactions.Wherein, connect between each reactor
The mode of connecing can be pipeline connection, be not limited thereto certainly.
High-temperature electrolysis water hydrogen manufacturing subsystem includes electrolytic tank of solid oxide (SOEC) 6 and photovoltaic generation unit, wherein light
It includes photovoltaic cell 10 to lie prostrate generator unit, converts the second light beam to electric energySpectrum can be efficiently utilized, photovoltaic cell is improved
Generating efficiency.Electrolytic tank of solid oxide 6 has conventional structure in this field, such as mainly by porous anode, solid electrolyte
It is formed with porous cathode, for carrying out high temperature electrolysis of steam hydrogen production reaction, reaction temperature is typically in the range of 800~950 DEG C.Its
In：
The electrolytic tank of solid oxide 6 is connected to photovoltaic cell 10, to utilize the electric energy of photovoltaic cell 10It is electrolysed
Hydrogen production reaction；
The electrolytic tank of solid oxide 6 is also thermally connected with oxidation reactor 4, and automatic oxidation reaction device 4 transmits heatExtremely
Electrolytic tank of solid oxide 6, to utilize vapor and carrier of oxygen MOxThe waste heat of reaction carries out electrolytic hydrogen production reaction；
The electrolytic tank of solid oxide 6 also with reoxidize 5 pipeline of reactor and connect, to carry to reoxidizing reactor conveying oxygen
Body MOyIt is fully oxidized required oxygen, further, current divider is provided on the pipeline, by electrolytic tank of solid oxide 6
The partial oxidation of generation, which is delivered to, reoxidizes reactor 5；
The electrolytic tank of solid oxide 6 is also connect with 4 pipeline of oxidation reactor, the hydrogen that oxidation reactor is exported and
The gaseous mixture of unreacted vapor is passed through, wherein unreacted vapor and the raw material as electrolytic hydrogen production, improve point of water
Xie Liang, hydrogen provide the reducing atmosphere to shield for porous cathode, improve the efficiency and effect of electrolytic hydrogen production.
Heat exchange subsystem is connect with reforming reaction unit, electrolytic tank of solid oxide by pipeline, to reforming reaction member
The hydrogen of hydrocarbon fuel, hydrogen and unreacted vapor and the electrolytic tank of solid oxide output of output and incomplete electricity
The heat of the vapor of solution is recycled；Further, using recycling heat to reform reaction member needed for methane and
Vapor is preheated, as an example, the heat exchange subsystem includes First Heat Exchanger 2, the second heat exchanger 7,8 and of third heat exchanger
4th heat exchanger 9, wherein：
First Heat Exchanger 2 exchanges heat the hydrocarbon fuel that room temperature methane and reduction reactor 3 export, and completes the pre- of methane
Heat；
Second heat exchanger 7 exchanges heat normal-temperature water and the hydrocarbon fuel after First Heat Exchanger 2, completes vapor
Level-one preheats；
Third heat exchanger 8 by after the second heat exchanger 7 vapor and the hydrogen that exports of electrolytic tank of solid oxide 6 and
The vapor not being electrolysed completely exchanges heat, and completes the two level preheating of vapor；
4th heat exchanger 9 is by the hydrogen and unreacted of vapor and oxidation reactor output after third heat exchanger
The gaseous mixture of vapor exchanges heat, and completes the three-level preheating of vapor, the gaseous mixture after the 4th heat exchanger 9 is passed through solid
In oxide body electrolytic cell, the temperature that electrolytic hydrogen production reacts is made to be less than vapor and carrier of oxygen MOxThe temperature of reaction, to aoxidize
The heat of reactor 4 is smoothly transferred to electrolytic tank of solid oxide.
The present invention also provides the method for using solar energy fuel preparation system as described above to carry out preparation of fuel, packets
It includes：
Step 1：Optically focused and frequency dividing are carried out to solar spectral, the first light beam and the second light beam are formed, wherein by the first light
Beam is converted into thermal energy, converts the second light beam to electric energy；
Step 2：Using the thermal energy three-step approach methane vapor reforming is carried out by raw material of methane, vapor and the carrier of oxygen
Hydrocarbon fuel and hydrogen is obtained by the reaction, and the heat of the hydrocarbon fuel, hydrogen and unreacted vapor is recycled,
Described in three-step approach methane-steam reforming include：Carrier of oxygen MOzHydrocarbon fuel and carrier of oxygen MO are generated with methane reactionx、
Vapor and carrier of oxygen MOxReaction generates MOyWith hydrogen and carrier of oxygen MOyIt is reacted with oxygen and generates carrier of oxygen MOz；
Step 3：The gaseous mixture of hydrogen and unreacted vapor is passed through electrolytic tank of solid oxide, utilizes the electric energy
And vapor and carrier of oxygen MOxThe waste heat of reaction carries out electrolytic hydrogen production reaction, to obtain hydrogen fuel and oxygen, and to described
The hydrogen of electrolytic tank of solid oxide output and the heat for the vapor not being electrolysed completely are recycled；
Step 4：Using the oxygen obtained by step 3 as carrier of oxygen MO in raw material and step 2yIt carries out reaction and generates the carrier of oxygen
MOz。
Wherein this method further includes using the heat recycled in step 2 and 3 to being passed through the reforming reaction unit
The step of methane and water vapour are preheated, specifically includes：The hydrocarbon fuel and room temperature methane are exchanged heat, methane is completed
Preheating；Hydrocarbon fuel after heat exchange is exchanged heat with normal-temperature water, completes the level-one preheating of vapor；It will be preheated through level-one
Vapor afterwards exchanges heat with the hydrogen and the vapor not being electrolysed completely, completes the two level preheating of vapor；It will be through two
Vapor after grade preheating exchanges heat with the gaseous mixture, completes the three-level preheating of vapor.
It is wherein exchanged heat by heat exchanger, the temperature of methane is made to reach carrier of oxygen MOzWith methane reaction required temperature；It is logical
Crossing heat exchange makes the temperature of vapor as possible close to the vapor and carrier of oxygen MOxReact required temperature；The carrier of oxygen MOxWith
The temperature that vapor occurs in oxidation reaction process is kept constant.
Below in conjunction with the preferred embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Description.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, belongs to the scope of protection of the invention.
Embodiment 1
1, system flow description and effect analysis
In the present embodiment, room temperature CH4With 82.0m3The flow velocity of/min exchanges heat in heat exchanger 2 and 3 product stream of reduction reactor
Complete preheating, CH after preheating4Carrier of oxygen CeO into reduction reactor 3 and reactor2Reaction generates CO, H2、CO2、H2O、
CeO1.8Equal products.Room temperature H2Elder generation changes with process in the heat exchanger 7 before O enters oxidation reactor 3 with the rate of 147.9L/min
Preheating is completed in 3 product stream of the reduction reactor heat exchange of hot device 2, then in heat exchanger 8 and 6 product stream of electrolytic tank of solid oxide
Heat exchange is completed two level and is preheated, and it is anti-into oxidation then to complete three-level preheating in heat exchanger 9 and the heat exchange of 4 product stream of oxidation reactor
Answer device 4, and with the CeO that enters oxidation reactor 41.8Reaction generates CeO1.951With a certain amount of H2.The H of oxidation reactor 42
The H not reacted completely2O enters electrolytic tank of solid oxide 6 with certain flow and is electrolysed, H2O is electrolyzed to produce H2And O2,
The thermal energy and electric energy of 6 water electrolysis hydrogen production of electrolytic tank of solid oxide are respectively from oxidation reactor 4 and photovoltaic cell 10, solid oxygen
6 electrolysate O of compound electrolytic cell2Oxidation reactor 4 and CeO are entered with certain flow by current divider 111.951Reaction generates
CeO2, CeO2It leaves and reoxidizes reactor 4 and be returned to reduction reactor 3.
2, system basic parameter
According to bibliography, the optical efficiency of sunlight optically focused frequency dividing is about 70% (optically focused effective solar energy energy after dividing
Amount is the 70% of all incident sunlights), wherein 20.5% solar spectral is used for PV cell power generations, 49.6% solar energy
Spectrum is for providing heat required for methane chemical chain is reformed.The Silicon photrouics of selected technology maturation generate electricity, and efficiently use light
Spectrum wavelength ranging from 600-900nm, in the photovoltaic efficiency 60% of this range of wavelengths.Remaining sunlight spectrum is used for thermal-arrest,
The collecting efficiency that light turns heat is 70%.The heat exchanger efficiency of present invention heat exchanger is 1, and each average reactor temperature is as shown in table 1, is
Each stream temperature of uniting and total flow are as shown in table 2, the operation of system normal pressure.
The mean temperature of each reactor of 1. system of table
| Reactor title | Temperature T (DEG C) |
| Reduction reactor 3 | 950 |
| Oxidation reactor 4 | 950 |
| Reoxidize reactor 5 | 960 |
| Electrolytic tank of solid oxide 6 | 940 |
Each stream temperature of 2. system of table and flow
Result of calculation shows that the gross energy when input sunlight is 55635.0kW, and wherein 27595.0kW spectral energies are used
In light and heat collection, it is converted into using thermal energyFor 19316.5kW, 11405.2kW spectral energies are used for photovoltaic generation, conversion
For electric energyFor 6843.0kW.It is 652.7kmol/h that system, which generates synthesis gas rate, and wherein CO is 214.5kmol/h, H2For
429.7kmol/h, system decomposition water generate pure H2Rate is 325.0kmol/h.Solar energy is converted into fuel efficiency ηsol-fuelIt can
Up to 42.1%.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical solution and advantageous effect
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of solar energy fuel preparation system of electric-thermal chemical cycle coupling, including：
Optically focused divides subsystem, and optically focused and frequency dividing are carried out to solar spectral, to form the first light beam and the second light beam；
Three-step approach methane vapor reforming subsystem, including：
Heat collection unit converts first light beam to thermal energy；And
Reforming reaction unit, including：
Reduction reactor is thermally connected with the heat collection unit, as carrier of oxygen MOzHydrocarbon fuel is generated with methane reaction and oxygen carries
Body MOxContainer；
Oxidation reactor, as vapor and carrier of oxygen MOxReaction generates MOyWith the container of hydrogen, and
Reactor is reoxidized, as carrier of oxygen MOyIt is reacted with oxygen and generates carrier of oxygen MOzContainer,
The wherein described reduction reactor is connected to oxidation reactor to convey MO to oxidation reactorx, the oxidation reactor connection
To reoxidize reactor with to reoxidize reactor convey MOy, it is described reoxidize reactor be connected to reduction reactor with to also
Former reactor conveys MOz；
High-temperature electrolysis water hydrogen manufacturing subsystem, including：
Photovoltaic generation unit converts second light beam to electric energy；And
Electrolytic tank of solid oxide is electrically connected with the photovoltaic generation unit, and with the oxidation reactor be thermally connected, as
The container that electrolytic hydrogen production reaction generates hydrogen fuel is carried out to vapor under the heat effect that oxidation reactor transmits；The solid
Oxidate electrolytic cell be further connected to it is described reoxidize reactor and oxidation reactor, to convey oxygen to reoxidizing reactor
And the gaseous mixture of the hydrogen of oxidation reactor output and unreacted vapor is passed through electrolytic tank of solid oxide；And
Exchange heat subsystem, is connect respectively by pipeline with the reforming reaction unit, electrolytic tank of solid oxide, to the reformation
Hydrocarbon fuel, hydrogen and the unreacted vapor of reaction member output and the hydrogen of electrolytic tank of solid oxide output
The heat of gas and the vapor not being electrolysed completely is recycled.
2. solar energy fuel preparation system according to claim 1, which is characterized in that the heat exchange subsystem utilizes recycling
The heat methane and water vapour that are passed through the reforming reaction unit are preheated, the heat exchange subsystem specifically wraps
It includes：
First Heat Exchanger completes methane for the hydrocarbon fuel of room temperature methane and reduction reactor output to exchange heat
Preheating；
Second heat exchanger completes vapor for normal-temperature water and the hydrocarbon fuel after First Heat Exchanger to exchange heat
Level-one preheats；
Third heat exchanger, for will be by the hydrogen and not of vapor and electrolytic tank of solid oxide output after the second heat exchanger
The vapor being electrolysed completely exchanges heat, and completes the two level preheating of vapor；And
4th heat exchanger, for will be by the hydrogen and unreacted of vapor and oxidation reactor output after third heat exchanger
The gaseous mixture of vapor exchanges heat, and completes the three-level preheating of vapor.
3. solar energy fuel preparation system according to claim 2, which is characterized in that the 4th heat exchanger is additionally coupled to
The gaseous mixture of hydrogen and unreacted vapor after the 4th heat exchanger is passed through solid by the electrolytic tank of solid oxide
In oxide body electrolytic cell.
4. solar energy fuel preparation system according to claim 1, which is characterized in that the carrier of oxygen MOzSelected from oxidation
It is one or more in cerium, zinc oxide, copper oxide, nickel oxide or the Ca-Ti ore type carrier of oxygen.
5. solar energy fuel preparation system according to claim 1, which is characterized in that the photovoltaic generation unit includes light
Lie prostrate battery.
6. solar energy fuel preparation system according to claim 1, it is characterised in that：
It is provided with current divider on the electrolytic tank of solid oxide and the pipeline reoxidized between reactor, by solid oxygen
The partial oxidation that compound electrolytic cell generates, which is delivered to, reoxidizes reactor；
The reactor that reoxidizes is thermally coupled to reduction reactor, to transmit heat to reduction reactor；
Using the spectrum that solar spectral medium wavelength range is 600~900nm as the second light beam, by its repercussions in solar spectral
Long spectrum is as the first light beam.
7. a kind of solar energy fuel preparation system using as described in claim 1 to 6 any one carries out the side of preparation of fuel
Method, including：
Step 1：Optically focused and frequency dividing are carried out to solar spectral, form the first light beam and the second light beam, wherein the first light beam is turned
Thermal energy is turned to, converts the second light beam to electric energy；
Step 2：Using the thermal energy three-step approach methane-steam reforming is carried out by raw material of methane, vapor and the carrier of oxygen
Hydrocarbon fuel and hydrogen are obtained, and the heat of the hydrocarbon fuel, hydrogen and unreacted vapor is recycled, wherein institute
Stating three-step approach methane-steam reforming includes：Carrier of oxygen MOzHydrocarbon fuel and carrier of oxygen MO are generated with methane reactionx, water steam
Gas and carrier of oxygen MOxReaction generates MOyWith hydrogen and carrier of oxygen MOyIt is reacted with oxygen and generates carrier of oxygen MOz；
Step 3：The gaseous mixture of hydrogen and unreacted vapor is passed through electrolytic tank of solid oxide, using the electric energy and
Vapor and carrier of oxygen MOxThe waste heat of reaction carries out electrolytic hydrogen production reaction, to obtain hydrogen fuel and oxygen, and to the solid
The hydrogen of oxidate electrolytic cell output and the heat for the vapor not being electrolysed completely are recycled；
Step 4：Using the oxygen obtained by step 3 as carrier of oxygen MO in raw material and step 2yIt carries out reaction and generates carrier of oxygen MOz。
8. the method according to the description of claim 7 is characterized in that this method further includes described using being recycled in step 2 and 3
The step of heat preheats the methane and water vapour that are passed through the reforming reaction unit, specifically includes：
The hydrocarbon fuel and room temperature methane are exchanged heat, the preheating of methane is completed；
Hydrocarbon fuel after heat exchange is exchanged heat with normal-temperature water, completes the level-one preheating of vapor；
Vapor after level-one preheats is exchanged heat with the hydrogen and the vapor not being electrolysed completely, completes vapor
Two level preheats；
Vapor after two level preheats is exchanged heat with the gaseous mixture, completes the three-level preheating of vapor.
9. according to the method described in claim 8, it is characterized in that, the gaseous mixture after heat exchange is passed through soild oxide
In electrolytic cell, so that the temperature of electrolytic hydrogen production reaction is less than vapor and carrier of oxygen MOxThe temperature of reaction.
10. according to the method described in claim 8, it is characterized in that：
The temperature of methane is set to reach carrier of oxygen MO by heat exchangezWith methane reaction required temperature；
Steam temperature is set to improve and close to itself and carrier of oxygen MO by heat exchangexReact required temperature；
The carrier of oxygen MOxTemperature in oxidation reaction process occurs with vapor is kept constant.
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